US20220183934A1 - Sunscreen compositions containing porous metal oxide spheres - Google Patents

Sunscreen compositions containing porous metal oxide spheres Download PDF

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US20220183934A1
US20220183934A1 US17/437,986 US202017437986A US2022183934A1 US 20220183934 A1 US20220183934 A1 US 20220183934A1 US 202017437986 A US202017437986 A US 202017437986A US 2022183934 A1 US2022183934 A1 US 2022183934A1
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range
derivatives
sunscreen composition
spheres
porous
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Bernd Herzog
Brigitte Lindemann
Chrisstian CREMER
Rupa Hiremath Darji
Liangliang QU
Keith TASK
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BASF SE
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BASF SE
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Assigned to BASF SE reassignment BASF SE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BASF CORPORATION
Assigned to BASF CORPORATION reassignment BASF CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: Darji, Rupa Hiremath
Assigned to BASF SE reassignment BASF SE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BASF GRENZACH GMBH
Assigned to BASF GRENZACH GMBH reassignment BASF GRENZACH GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HERZOG, BERND, CREMER, CHRISTIAN, LINDEMANN, BRIGITTE
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/025—Explicitly spheroidal or spherical shape
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/0279—Porous; Hollow
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    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
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    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27—Zinc; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/368—Carboxylic acids; Salts or anhydrides thereof with carboxyl groups directly bound to carbon atoms of aromatic rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
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    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
    • A—HUMAN NECESSITIES
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    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
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    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
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    • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
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    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
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    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
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    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes
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    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52—Stabilizers
    • A61K2800/522—Antioxidants; Radical scavengers
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    • A61K2800/65—Characterized by the composition of the particulate/core
    • A61K2800/651—The particulate/core comprising inorganic material

Definitions

  • the present invention relates to a method for increasing sun protection factor (SPF) of a sunscreen composition, use of porous metal oxide spheres for increasing SPF of a sunscreen composition and preparation of sunscreen compositions comprising the porous spheres.
  • SPPF sun protection factor
  • Sunscreen compositions are used to shield human skin from the damage of solar radiations.
  • Sunscreen compositions having high UV protection are required to prevent adverse effects of solar radiations, particularly those of the UV radiations.
  • Wide varieties of UV absorbers are available for use in sunscreen compositions.
  • the object can be achieved by addition of porous spheres (e.g., microspheres) comprising a metal oxide to a sunscreen composition, which increases the SPF of the sunscreen composition.
  • porous spheres e.g., microspheres
  • the main aspect of the presently claimed invention is to provide a method for increasing the SPF of a sunscreen composition.
  • the method comprises adding porous spheres (e.g., microspheres) comprising a metal oxide to the sunscreen composition, wherein the metal oxide is at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxides, zinc oxide, indium oxide, tin oxide and chromium oxide.
  • porous spheres comprising a metal oxide for increasing the sun protection factor of a sunscreen composition
  • the metal oxide is at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxides, zinc oxide, indium oxide, tin oxide and chromium oxide.
  • the presently claimed invention provides a sunscreen composition
  • a sunscreen composition comprising water and the porous spheres (e.g., microspheres) comprising a metal oxide in the range of 0.1 to 10.0 weight-%, based on total weight of the sunscreen composition, wherein the metal oxide is at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxides, zinc oxide, indium oxide, tin oxide and chromium oxide.
  • FIG. 1 is a scanning electron microscope (SEM) image of a porous silica sphere, according to an embodiment of the invention.
  • FIG. 2 is a SEM image of a porous silica sphere, according to an embodiment of the invention.
  • FIG. 3 is a SEM image of a porous titania sphere, according to an embodiment of the invention.
  • FIG. 4 is a SEM image of a porous titania sphere, according to an embodiment of the invention.
  • FIG. 5 depicts a graph related to absorbance of aqueous dispersions comprising Patent Blue V in the presence of porous silica spheres.
  • FIG. 6 depicts a graph related to UV absorbance of aqueous dispersions comprising benzophenone-4 in the presence of porous silica spheres.
  • FIG. 7 depicts a graph related to UV absorbance ⁇ max of aqueous dispersions comprising benzophenone-4 in the presence of varying amounts of porous silica spheres.
  • FIG. 8 depicts a graph related to UV absorbance ⁇ max of aqueous dispersions comprising benzophenone-4 in the presence of commercial sample of Sunsil® 130.
  • FIG. 9 depicts a graph related to absorbance of aqueous dispersions comprising Patent Blue V in the presence of porous titania spheres.
  • FIG. 10 depicts a graph related to UV absorbance of aqueous dispersions comprising porous titania spheres.
  • FIG. 11 depicts a graph related to the absorbance of sunscreen compositions comprising UV filters in the absence and the presence of porous silica spheres.
  • FIG. 12 depicts a graph related to the absorbance of sunscreen compositions without an additional UV filter in the absence and the presence of porous silica spheres.
  • FIG. 13 depicts a chart related to the whitening effect of sunscreen compositions comprising UV filters in the absence and the presence of porous silica spheres.
  • FIG. 14 depicts a chart related to the whitening effect of sunscreen compositions without an additional UV filter in the absence and the presence of porous silica spheres.
  • a group is defined to comprise at least a certain number of embodiments, this is meant to also encompass a group which preferably consists of these embodiments only.
  • the terms ‘first’, ‘second’, ‘third’ or ‘a’, ‘b’, ‘c’, etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the presently claimed invention described herein are capable of operation in other sequences than described or illustrated herein.
  • first’, ‘second’, ‘third’ or ‘(A)’, ‘(B)’ and ‘(C)’ or ‘(a)’, ‘(b)’, ‘(c)’, ‘(d)’, ‘i’, ‘ii’ etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, that is, the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application as set forth herein above or below.
  • porous spheres e.g., microspheres
  • a metal oxide e.g., a metal oxide
  • the resultant sunscreen composition does not show the whitening effect usually associated with the addition of scattering particles.
  • the presently claimed invention provides sunscreen compositions having a high SPF and a low whitening.
  • porous metal oxide spheres scatter the light passing through a sunscreen composition.
  • porous metal oxide spheres e.g., microspheres
  • the presence of porous metal oxide spheres (e.g., microspheres) in a sunscreen composition leads to an overall increase in the pathlength of the light travelling through the sunscreen layer. Consequently, the photon absorption by the UV filter or dye molecules present in the sunscreen composition increases. Thus, an overall increase in absorbance of the dye or the UV absorber is achieved without increasing its concentration.
  • the main aspect of the presently claimed invention is to provide a method for increasing the sun protection factor of a sunscreen composition.
  • the method comprises adding porous spheres (e.g., microspheres) comprising a metal oxide to the sunscreen composition, wherein the metal oxide is preferably at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxides, zinc oxide, indium oxide, tin oxide and chromium oxide.
  • the metal oxide is at least one selected from the group consisting of silica, zinc oxide and titania.
  • the metal oxide is silica.
  • titania is another embodiment selected from the group consisting of titania.
  • porous spheres comprising a metal oxide for increasing the sun protection factor of a sunscreen composition
  • the metal oxide is preferably at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxides, zinc oxide, indium oxide, tin oxide and chromium oxide.
  • the metal oxide is at least one selected from the group consisting of silica, zinc oxide and titania. In another embodiment, the metal oxide is silica. In yet another embodiment, the metal oxide is titania.
  • the porous spheres comprise an additional light absorber.
  • the additional light absorber is carbon black powder.
  • microspheres are spherical or spherical-like microparticles with average diameter or particle size typically ranging from 1 ⁇ m to 1000 ⁇ m (1 mm). Examples of microspheres include glass microspheres and polyethylene microspheres.
  • the SPF factor (sun protection factor, SPF) serves to evaluate light protection preparations (sunscreen compositions) on humans (in vivo). It indicates how much longer a person with a sunscreen agent can be exposed to the sun without suffering sunburn than would be possible with the particular individual's self-protection time.
  • the SPF is determined in vitro by measuring the diffuse transmission in the spectral range between 290 and 400 nm.
  • the term “monodisperse” in reference to spheres, microspheres or nanospheres means particles having generally uniform shapes and generally uniform diameters.
  • a present monodisperse population of spheres, microspheres or nanospheres may have 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% of the particles by number having diameters within ⁇ 7%, ⁇ 6%, ⁇ 5%, ⁇ 4%, ⁇ 3%, ⁇ 2% or ⁇ 1% of the average diameter of the population.
  • particle size is synonymous with particle diameter and is determined for instance with scanning electron microscopy (SEM) or transmission electron microscopy (TEM). Average particle size is synonymous with D50, meaning half of the population resides above this point, and half below. Particle size refers to primary particles. Particle size may be measured by laser light scattering techniques, with dispersions or dry powders.
  • the porous spheres are present in an amount in the range of 0.1 to 10.0 weight-%, or in the range of 1.0 to 8.0 weight-%, or in the range of 2.0 to 7.0 weight-%, based on total weight of the sunscreen composition.
  • the porous spheres e.g., microspheres
  • the porous spheres are present in an amount of 5.5 weight-%, based on total weight of the sunscreen composition.
  • the porous spheres e.g., microspheres
  • the porous spheres are present in an amount of 2.0 weight-%, based on total weight of the sunscreen composition.
  • the amount of the metal oxide in the porous spheres is in the range of 60.0 to 99.9 weight-%, or in the range of 65.0 to 99.0 weight-%, or in the range of 75.0 to 98.0 weight-% or in the range of 80.0 to 95.0 weight-%, based on total weight of the porous spheres.
  • the porous spheres have an average diameter in the range of 0.5 ⁇ m to 100.0 ⁇ m; or in the range of 1.0 ⁇ m to 90.0 ⁇ m; or in the range of 5.0 ⁇ m to 80.0 ⁇ m; or in the range of 10.0 ⁇ m to 70.0 ⁇ m; or in the range of 20.0 ⁇ m to 50.0 ⁇ m.
  • the porous spheres have an average porosity in the range of 0.10 to 0.90.
  • the porous spheres have an average porosity in the range of 0.10 to 0.80, or in the range of 0.30 to 0.80; or in the range of 0.15 to 0.75; or in the range of 0.25 to 0.60; or in the range of 0.30 to 0.50.
  • the porous spheres are monodisperse.
  • the porous spheres have an average pore diameter in the range of 50 nm to 999 nm; or in the range of 100 nm to 900 nm; or in the range of 200 nm to 800 nm; or in the range of 300 nm to 700 nm; or in the range of 400 nm to 600 nm.
  • the porous spheres have more than one population of pores each having an average pore diameter, wherein each population has a different average pore diameter. In another embodiment, the porous spheres have two population of pores each having an average pore diameter.
  • the porous spheres are configured to form the porous spheres.
  • a. have an average diameter in the range of 0.5 ⁇ m to 100.0 ⁇ m;
  • c. have an average pore diameter in the range of 50 nm to 999 nm and
  • d. are monodisperse.
  • the porous spheres are configured to form the porous spheres.
  • the porous metal oxide spheres are prepared using a polymeric sacrificial template.
  • the porous spheres are prepared, e.g., by a method comprising the following steps.
  • a liquid dispersion of polymer particles (e.g., nanoparticles) and a metal oxide is formed. Liquid droplets of the dispersion are formed. The liquid droplets are dried to provide polymer template spheres (e.g., microspheres) comprising polymer spheres and metal oxide. The polymer spheres are removed from the template spheres to provide the porous metal oxide spheres.
  • polymer template spheres e.g., microspheres
  • Another method for the preparation of the porous spheres having at least two different average particle sizes comprises the following steps.
  • a liquid solution or dispersion of monodisperse polymer particles (e.g., nanoparticles) is formed. At least one further liquid solution or dispersion of monodisperse polymer particles (e.g., nanoparticles) is formed. The average diameters of the monodisperse polymer particles of each of the solutions or dispersions are different.
  • Each of the solutions or dispersions are mixed together; wherein a metal oxide is added to one or more of the solutions or dispersions and/or wherein a metal oxide is added to the mixture, to obtain a final liquid dispersion of polymer particles and a metal oxide.
  • Liquid droplets of the final liquid dispersion are formed.
  • the liquid droplets are dried to provide polymer template spheres comprising monodisperse polymer spheres having bimodal distribution and the metal oxide.
  • the polymer spheres are removed from the template spheres to provide the porous metal oxide spheres which are typically microspheres.
  • the method comprises forming a liquid dispersion of polymer particles (e.g., nanoparticles) and the metal oxide, spray-drying the liquid dispersion to provide polymer template spheres and removing the polymer spheres from the template spheres.
  • polymer particles e.g., nanoparticles
  • the method comprises providing a continuous phase and mixing the liquid dispersion with the continuous phase to form an emulsion containing dispersed liquid dispersion droplets and collecting the droplets.
  • the drying involves microwave irradiation, oven drying, drying under vacuum, drying in the presence of a desiccant, or a combination thereof.
  • a weight ratio of the polymer particles (e.g., nanoparticles) to the metal oxide is in the range of 0.5:1 to 10.0:1.
  • the polymer is selected from the group consisting of poly(meth)acrylic acid, poly(meth)acrylates, polystyrenes, polyacrylamides, polyethylene, polypropylene, polylactic acid, polyacrylonitrile, derivatives thereof, salts thereof, copolymers thereof and combinations thereof.
  • the polymer spheres e.g., nanospheres
  • the template spheres e.g., microspheres
  • the polymer spheres e.g., nanospheres
  • the template spheres e.g., microspheres
  • porous spheres comprising a metal oxide are spherical or spherical-like and are micron-scaled.
  • the polymer particles employed as template are spherical, nano-scaled and are monodisperse.
  • the metal oxide employed may also be in particle form and having nano-scaled particles. Drying of the polymer/ metal oxide droplets followed by removal of the polymer provides microspheres having uniform voids (pores). Thus, the porous metal oxide spheres contain uniform pore diameters as a result of the polymer particles being porous and monodisperse.
  • the pore diameters are dependent on the size of the polymer particles. Some shrinkage or compaction may occur upon polymer removal, providing pore sizes somewhat smaller than the original polymer particle size, for example from 10% to 40% smaller than the polymer particle size.
  • the pore diameters are uniform as are the polymer particle shape and size.
  • the sunscreen composition further comprises an UV absorber selected from the group consisting of:
  • benzophenone-3 (2-hydroxy-4-methoxybenzophenone); benzophenone-4 (2-hydroxy-4-methoxybenzophenone-5-sulfonic acid); benzophenone-8 (2,2′-dihydroxy-4-methoxybenzo-phenone); or amino-substituted hydroxybenzophenones of the formula
  • R 1 and R 2 denote hydrogen, C 1 -C 20 -alkyl, C 2 -C 10 -alkenyl, C 3 -C 10 -cycloalkyl, C 3 -C 10 -cycloalkenyl, wherein the substituents R 1 and R 2 together with the nitrogen atom to which they are bonded can form a 5- or 6-membered ring;
  • R 3 and R 4 independently of each other denote C 1 -C 20 -alkyl; C 2 -C 10 -alkenyl; C 3 -C 10 -cycloalkyl;
  • X denotes hydrogen; COOR 5 ; or CONR 6 R 7 ;
  • R 5 , R 6 , R 7 independently of each other denote hydrogen; C 1 -C 20 -alkyl; C 2 -C 10 -alkenyl; C 3 -C 10 -cycloalkyl; C 3 -C 10 -cycloalkenyl; (Y—O) o -Z; or aryl;
  • Z denotes —CH 2 —CH 3 ; —CH 2 —CH 2 —CH 3 ; —CH 2 —CH 2 —CH 2 —CH 3 ; or —CH(CH 3 )—CH 3 ;
  • n denotes 0 to 3;
  • n denotes 0 to 4.
  • o denotes 1 to 20.
  • the UV absorber is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid.
  • R 1 and R 2 independently of each other denote C 1 -C 20 -alkyl; C 2 -C 20 -alkenyl; C 3 -C 10 -cycloalkyl;
  • R 3 denotes alkylene, cycloalkylene, alkenylene or phenylene optionally substituted by a carbonyl or carboxyl group; a biradical of the formula (HBP-03a) *—CH 2 —C ⁇ C—CH 2 —*; or
  • n 2 denotes a number from 1 to 3;
  • A denotes —O—; or —N(R 5 )—;
  • R 5 denotes hydrogen; C 1 -C 5 -alkyl; or hydroxy-C 1 -C 5 -alkyl;
  • UV absorbers (d 3 ) can preferably be employed as UV absorbers (d 3 ).
  • dibenzoylmethane derivatives (d 4 ) which can be employed according to the invention are butylmethoxydibenzoylmethane-[1-(4-tert-butylphenyl)-3-(4-methoxy-phenyl)propane-1,3-dione].
  • diphenylacrylate derivatives (d 5 ) which can be employed according to the invention are octocrylene-(2-ethylhexyl 2-cyano-3,3′-diphenylacrylate) or etocrylene (ethyl 2-cyano-3,3′-diphenylacrylate).
  • benzofuran derivatives (d 7 ) which can be employed according to the invention are 3-(benzofuranyl) 2-cyanoacrylate, 2-(2-benzofuranyl)-5-tert-butylbenzoxazole or 2-(p-aminophenyl)benzofuran and in particular the compounds of the formula
  • polymeric UV absorbers (d 3 ) which can be employed according to the invention and contain one or more organosilicon radicals are benzylidenemalonate derivatives, in particular the compound of the formula
  • R 24 denotes hydrogen or methoxy and r denotes approximately 7; the compound of the formula
  • cinnamic acid esters (d 9 ) which can be employed according to the invention are octyl methoxycinnamate (4-methoxycinnamic acid 2-ethylhexyl ester), diethanolamine methoxycinnamate (diethanolamine salt of 4-methoxycinnamic acid), isoamyl p-methoxycinnamate (4-ethoxycinnamic acid 2-isoamyl ester), 2,5-diisopropyl methycinnamate or a cinnamic acid amido derivative.
  • camphor derivatives (d 10 ) which can be used according to the invention are 4-methylbenzylidenecamphor [3-(4′-methyl)benzylidenebornan-2-one], 3-benzylidenecamphor (3-benzylidenebornan-2-one), polyacrylamidomethylbenzylidenecamphor ⁇ N-[2(and 4)-2-oxyborn-3-ylidenemethyl)benzyl]acrylamide polymer ⁇ , trimoniumbenzylidenecamphor sulfate-[3-(4′-trimethylammonium)-benzylidenebornan-2-one methylsulfate], tereph-thalydenedicamphorsulfonic acid ⁇ 3,3′-(1,4-phenylenedimethine)-bis-(7,7-dimethyl-2-oxobicyclo-[2.2.1]heptane-1-methanesulfonic acid ⁇ or salts thereof, or benzylidenecamphorsulfonic acid
  • hydroxyphenyltriazine derivatives (d 11 ) which can be used according to the invention are, in particular, bis-resorcinyltriazines of the formula
  • R 1 and R 2 independently of each other denote hydrogen; C 1 -C 18 -alkyl; C 2 -C 18 -alkenyl; a radical of the formula —CH 2 —CH(—OH)- 13 CH 2 —O-T 1 ; a radical of the formula
  • R 3 , R 4 and R 5 independently of each other denote hydroxyl; C 1 -C 5 -alkoxy which is unsubstituted or substituted by one or more OH groups; amino; mono- or di-C 1 -C 5 -alkylamino; M; a radical of the formula
  • R 10 , R 11 and R 12 independently of each other denote C 1 -C 14 -alkyl which is unsubstituted or substituted by one or more OH groups;
  • R 13 denotes hydrogen; M; C 1 -C 5 -alkyl; or a radical of the formula —(CH 2 ) m3 —O-T 1 ;
  • R 6 denotes the direct bond; a straight-chain or branched C 1 -C 4 -alkylene radical; or a radical of the formula —C m4 H 2m4 , or —C m4 H 2m4 —O—;
  • R 7 , R 8 and R 9 independently of each other denote C 1 -C 13 -alkyl; C 1 -C 18 -alkoxy or a radical of the formula
  • R 14 denotes C 1 -C 5 -alkyl
  • M denotes a metal cation
  • T 1 denotes hydrogen; or (C 1 -C 8 )-alkyl
  • n 1 , m 2 and m 3 independently of each other denote 1 to 3;
  • n 4 denotes 2 to 14;
  • p 1 denotes 0 or a number from 1 to 5.
  • R 1 denotes hydrogen; C 1 -C 12 -alkyl; C 1 -C 12 -alkoxy; C 1 -C 12 -alkoxycarbonyl; C 5 -C 10 -cycloalkyl or —S0 3 M;
  • R 3 denotes hydrogen; C 1 -C 18 -alkyl; C 1 -C 12 -alkoxy; or halogen;
  • n denotes 1 or 2;
  • R 2 denotes C 1 -C 20 -alkyl; C 5 -C 10 -cyclo-C 1 -C 5 -alkyl; C 1 -C 12 -alkoxy-C 1 -C 5 -alkyl; C 5 -C 10 -cyclo-alkoxy-C 1 -C 5 -alkyl; C 6 -C 10 -aryl; C 6 -C 10 -aryl-C 1 -C 5 -alkyl;
  • R 2 denotes the direct bond; or —(CH 2 ) p —;
  • p is an integer from 1 to 3.
  • R 1 denotes C 1 -C 12 -alkyl; or —S0 3 M;
  • R 3 denotes hydrogen; halogen, preferably Cl;
  • n denotes 1;
  • R 2 C 1 -C 12 -alkyl
  • p denotes 1 to 3;
  • preferred UV filters of the formula BT-01 are those wherein
  • R 1 denotes hydrogen
  • R 3 denotes C 1 -C 13 -alkyl
  • n 2;
  • R 2 denotes —CH 2 —.
  • trianilino-s-triazine derivatives (d 13 ) which can be used according to the invention correspond to the formula
  • R 1 , R 2 and R 3 independently of each other denote optionally substituted C 1 -C 20 -alkyl, aryl or hetaryl;
  • X denotes O; or NR 4 ;
  • R 4 denotes hydrogen; or optionally substituted C 1 -C 20 -alkyl, aryl or hetaryl.
  • a particularly preferred representative of this compound class is Ethylhexyl Triazone corresponding to the formula
  • Preferred tris-biphenyl-triazine derivatives (d 17 ) which can be used according to the invention correspond to the formula
  • A denotes a radical of the formula
  • R 1 and R 5 independently of each other denote hydrogen; C 1 -C 18 -alkyl; or C 1 -C 12 -aryl;
  • R 2 , R 3 and R 4 independently of each other denote hydrogen; or a radical of the formula
  • R 6 , R 7 , R 8 , R 9 and R 10 independently of each other denote hydrogen; hydroxyl; halogen; C 1 -C 18 -alkyl; C 1 -C 18 -alkoxy; C 6 -C 12 -aryl; biphenylyl; C 6 -C 12 -aryloxy; C 1 -C 18 -alkylthio; carboxyl; —COOM; C 1 -C 18 -alkylcarboxyl; aminocarbonyl; or mono- or di-C 1 -C 18 -alkylamino; C 1 -C 10 -acylamino; —COOH;
  • M denotes an alkali metal ion
  • x denotes 1 or 2;
  • y denotes an integer from 2 to 10.
  • the UV filters (d 17 ) which can be used according to the invention correspond to the compounds of the formula
  • Preferred benzylidenemalonates (d 19 ) which can be employed according to the invention correspond to the formula
  • R 1 denotes methyl; ethyl; propyl; or n-butyl
  • R denotes tert butyl
  • R 2 and R 3 independently of each other hydrogen; or methyl
  • R 4 methyl; ethyl; or n-propyl
  • R 5 and R 6 independently of each other hydrogen; or C 1 -C 3 -alkyl
  • R 1 denotes ethyl; propyl; or n-butyl
  • R denotes isopropyl
  • benzylidenemalonates which can be used according to the invention R 1 R (MBM-02) methyl (MBM-03) methyl (MBM-04) methyl (MBM-05) methyl (MBM-06) methyl (MBM-07) methyl (MBM-08) methyl (MBM-09) methyl (MBM-10) methyl (MBM-11) ethyl (MBM-12) propyl (MBM-13) n-butyl (MBM-14) methyl (MBM-15) methyl (MBM-02) methyl (MBM-03) methyl (MBM-04) methyl (MBM-05) methyl (MBM-06) methyl (MBM-07) methyl (MBM-08) methyl (MBM-09) methyl (MBM-10) methyl (MBM-11) ethyl (MBM-12) propyl (MBM-13) n-butyl (MBM-14) methyl (MBM-15) methyl
  • diarylbutadiene derivatives (d 23 ) is 1,1-dicarboxy-(2,2 7 -di-methylpropyl)-4,4-diphenylbutadiene.
  • Each of the abovementioned UV filters (d 1 )-(d 23 ) can be used according to the invention as a mixture.
  • mixtures of two, three, four, five or six of the filter groups (d 1 )-(d 23 ) can be used according to the invention.
  • Mixtures of two, three, four, five or six UV filters from one or more representatives of substance classes (d 1 )-(d 23 ) can also be used according to the invention.
  • UV filters (d) are representatives of the following compound classes:
  • oil-soluble UV filters are used according to the invention:
  • the UV filter is at least one selected from the group consisting of
  • the UV filter is a mixture of UV filters selected from the group consisting of (d 9a ), (d 11a ), (d 13a ) and (d 3a ).
  • porous metal oxide spheres e.g., microspheres
  • the method further minimizes or masks the whitening effect of the sunscreen composition and maintains its transparency.
  • the use further minimizes or masks the whitening effect of the sunscreen composition and maintains its transparency.
  • the whitening effect of a sunscreen composition is determined by test based on the assessment of light transmittance through a thin film of sunscreen sample spread on roughened substrate.
  • the presently claimed invention provides a sunscreen composition, comprising water and porous spheres (e.g., microspheres) comprising a metal oxide in the range of 1.0 to 10.0 weight-%, based on total weight of the sunscreen composition, wherein the metal oxide is at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxides, zinc oxide, indium oxide, tin oxide and chromium oxide.
  • a sunscreen composition comprising water and porous spheres (e.g., microspheres) comprising a metal oxide in the range of 1.0 to 10.0 weight-%, based on total weight of the sunscreen composition, wherein the metal oxide is at least one selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxides, zinc oxide, indium oxide, tin oxide and chromium oxide.
  • the metal oxide is at least one selected from the group consisting of silica, zinc oxide and titania. In another embodiment, the metal oxide is silica. In yet another embodiment, the metal oxide is titania.
  • the porous silica spheres have a refractive index in the range from 1.4 to 1.5.
  • the porous silica spheres are incorporated in a sunscreen composition having refractive index in the same range, e.g. from 1.3 to 1.6, the porous silica spheres do not affect the appearance of the sunscreen composition.
  • the amount of the metal oxide in the porous spheres is in the range of 60.0 to 99.9 weight-%, or in the range of 75.0 to 98.0 weight-% or in the range of 80.0 to 95.0 weight-%, based on total weight of the porous spheres.
  • the sunscreen composition comprises porous spheres having an average diameter in the range of 0.5 ⁇ m to 100.0 ⁇ m; or 1.0 ⁇ m to 90.0 ⁇ m; or in the range of 5.0 ⁇ m to 80.0 ⁇ m; or in the range of 10.0 ⁇ m to 70.0 ⁇ m; or in the range of 20.0 ⁇ m to 50.0 ⁇ m.
  • the porous spheres have an average porosity in the range of 0.10 to 0.90.
  • the sunscreen composition comprises porous spheres having an average porosity in the range of 0.10 to 0.80, or in the range of 0.30 to 0.80; or in the range of 0.15 to 0.75; or in the range of 0.25 to 0.60; or in the range of 0.30 to 0.50.
  • the sunscreen composition comprises porous spheres have an average pore diameter in the range of 50 nm to 999 nm; or in the range of 100 nm to 900 nm; or in the range of 200 nm to 800 nm; or in the range of 300 nm to 700 nm; or in the range of 400 nm to 600 nm.
  • the porous spheres are monodisperse.
  • the porous spheres are configured to form the porous spheres.
  • the sunscreen composition comprises porous spheres
  • a. have an average diameter in the range of 0.5 ⁇ m to 100.0 ⁇ m;
  • c. have an average pore diameter in the range of 50 nm to 999 nm;
  • d. are monodisperse.
  • the sunscreen composition further comprises an UV absorber selected from the group consisting of:
  • UV absorbers are described hereinabove.
  • the sunscreen composition further comprises a dye selected from the group consisting of acid violet 43 and acid red 33.
  • the sunscreen composition further comprises a discontinuous oil phase in the range of 5.0 to 50.0 weight-%, based on total weight of the sunscreen composition.
  • possible oily substances are, for example, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms (e.g. Eutanol0 G), esters of linear C 6 -C 22 -fatty acids with linear or branched C 6 -C 22 -fatty alcohols and esters of branched C 6 -C 13 -carboxylic acids with linear or branched C 6 -C 22 -fatty alcohols, such as e.g.
  • propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols triglycerides based on C 6 -C 10 -fatty acids, liquid mono/di/triglyceride mixtures based on C 6 -C 18 -fatty acids, esters of C 6 -C 22 -fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C 2 -C 12 -dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, plant oils, branched primary alcohols, substituted cyclohexanes, linear and branched C 6 -C 22 -fatty alcohol carbonates, such as e.g.
  • Dicaprylyl Carbonate (Cetio® GE), Guerbet carbonates based on fatty alcohols having 6 to 18 preferably 8 to 10 C atoms, esters of benzoic acid with linear and/or branched C 6 -C 22 -alcohols (e.g. Finsolv® TN), linear or branched, symmetric or unsymmetric dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as e.g.
  • Dicaprylyl Ether (Cetiol° GE), ring-opening products of epoxidized fatty acid esters with polyols (Hydagen® HSP, Sovermol® 750, Sovermol® 1102), silicone oils (cyclomethicone, silicon methicone types and others) and/or aliphatic or naphthenic hydrocarbons, such as e.g. mineral oil, Vaseline, petrolatum, squalene, squalene, iso-hexadecane or dialkylcyclohexanes are suitable in consideration.
  • silicone oils cyclomethicone, silicon methicone types and others
  • aliphatic or naphthenic hydrocarbons such as e.g. mineral oil, Vaseline, petrolatum, squalene, squalene, iso-hexadecane or dialkylcyclohexanes are suitable in consideration.
  • the oily substances are medium-polarity oils, in particular esters of C 2 -C 12 -dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms and/or linear and branched C 6 -C 22 -fatty alcohol carbonates, Adipic acid esters of linear or branched alcohols having 1 to 22 carbon atoms, very particularly of linear alcohols having 1 to 6 carbon atoms, are particularly suitable here.
  • Linear and branched fatty alcohol carbonates are particularly preferably used as oily substance.
  • dibutyl adipate is used as oily substance.
  • the amount of oil phase is in the range of 20 to 35 weight-%, based on total weight of the sunscreen composition.
  • the sunscreen composition further comprises at least one emulsifier in the range of 1.0 to 20.0 weight-%, based on total weight of the sunscreen composition.
  • the emulsifier is selected from the group consisting of an anionic emulsifier, a nonionic emulsifier and a polymeric emulsifier.
  • the anionic surfactants are characterized by one or more anionic group which confers solubility in water, such as e.g. a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic radical.
  • the molecule can contain polyglycol ether, ester, ether and hydroxyl groups.
  • Anionic surfactants which are tolerated by skin are known to the person skilled in the art in large numbers from relevant handbooks and are commercially obtainable.
  • anionic surfactants are, in each case in the form of their salts, ether-carboxylic acids, acylsarcosides having 8 to 24 C atoms in the acyl group, acyltaurides having 8 to 24 C atoms in the acyl group, acylisethionates having 8 to 24 C atoms in the acyl group, sulfosuccinic acid mono- and dialkyl esters having 8 to 24 C atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters having 8 to 24 C atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 8 to 24 C atoms, linear alpha-olefinsulfonates having 8 to 24 C atoms, alpha-sulfo-fatty acid methyl esters of fatty acids having 8 to 30 C atoms, alkyl sulfates
  • the salts of these surfactants are preferably selected from the sodium, potassium and ammonium and the mono-, di- and trialkanalammonium salts having 2 to 4 C atoms in the alkanol group.
  • anionic surfactants are liquid at room temperature, preferably from 18 to 25° C.
  • a desirable feature in particular of these anionic surfactants is that they have a low water content of at most 10 wt. %, preferably 0.1 to 5 weight-%, based on the total weight of the anionic surfactant.
  • the anionic surfactants are alk(en)yl polyglycol ether citrates and in particular mixtures of mono-, di- and triesters of citric acid and alkoxylated alcohols which correspond to the formula (I):
  • R 1 , R 2 and R 3 independently of each other denote hydrogen or the radical of the formula (II) R 4 (OCH 2 CHR 5 ) n
  • R represents a linear or branched alkyl and/or alkenyl radical having 6 to 22 carbon atoms
  • R 5 represents hydrogen or a methyl radical
  • n a number from 1 to 20, with the condition that at least one of the radicals
  • R 1 , R 2 or R 3 is other than hydrogen.
  • Typical examples of the alcohol part of the esters are addition products of on average 1 to 20 mol, preferably 5 to 10 mol of ethylene oxide and/or propylene oxide on caproyl alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitolelyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical grade mixtures thereof.
  • alk(en)yl polyglycol ether citrates are advantageous for the agents according to the invention since they are liquid anionic surfactants having a low water content of max. 5 wt. %, based on the anionic surfactant.
  • the anionic surfactants are preferably present in amounts in the range of 7 to 17 weight-%, based on total weight of the sunscreen composition.
  • the agents according to the invention furthermore comprise at least (c) 0.5 to 25 wt. % of a further co-surfactant which differs from anionic surfactants.
  • Suitable co-surfactants are, in principle, zwitterionic, ampholytic, cationic and/or nonionic surfactants.
  • zwitter-ionic surfactants which carry at least one quaternary ammonium group and at least one —COO(—) or —SO 3 (—) group in the molecule are called zwitter-ionic surfactants.
  • Particularly suitable zwitter-ionic surfactants are the so-called betaines, such as the N-alkyl-N,N-dimethylammonium glycinates, for example coco-alkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, for example coco-acylamimopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazoline having in each case 8 to 18 C atoms in the alkyl or acyl group, and coco-acylaminoethylhydroxy-ethylcarboxymethyl glycinate.
  • Tego® Betain 810 (INCI: Capryl/Capramidopropyl Betaine) and a surfactant mixture of Rewopol° SBCS 50K (INCI: Disodium PEG-5 Laurylcitrate Sulfosuccinate, Sodium Laureth Sulfate) and Tego° Betain 810 (Capryl/Capramidopropyl Betaine), in particular in the weight ratio of 1:4 to 4:1, very particularly preferably in the weight ratio of from 1:4 to 1:1, are particularly preferred according to the invention.
  • Ampholytic surfactants are understood as meaning those surface-active compounds which contain, apart from a C 8 -C 18 -alkyl or acyl group, at least one free amino group and at least one —COOH or —SO 3 H group in the molecule and are capable of formation of inner salts.
  • ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids having in each case about 8 to 18 C atoms in the alkyl group.
  • Preferred ampholytic surfactants are N-coco-alkylaminopropionate, coco-acylaminoethylaminopropionate and C 12 -C 18 acylsarcosine.
  • Quaternary ammonium compounds in particular can be used as cationic surfactants.
  • Surfactants from this substance class have a particularly high affinity for the skin and can improve the degree of sensory smoothness.
  • These include, inter alfa, ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride.
  • the very readily biodegradable quaternary ester compounds such as, for example, the dialkylammonium methosulfates and methylhydroxyalkyldialkoyloxyalkylammonium methosulfates marketed under the trade name Stepantex ® and the corresponding products of the Dehyquart° series, can furthermore be employed as cationic surfactants.
  • esterquats is in general understood as meaning quaternized fatty acid triethanolamine ester salts. They impart to the compositions particularly soft feel. These are known substances which are prepared by the relevant methods of organic chemistry. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.
  • Nonionic surfactants are particularly preferably present as co-surfactants, for example
  • the addition products of ethylene oxide and/or of propylene oxide on fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or on castor oil are known, commercially obtainable products.
  • These are homologue mixtures, the average degree of alkoxylation of which corresponds to the ratio of the substance amounts of ethylene oxide and/or propylene oxide and substrate with which the addition reaction is carried out. They are W/O or 0/W emulsifiers, depending on the degree of ethoxylation.
  • the reaction products with 1 -100 mol of ethylene oxide are particularly suitable.
  • compositions from the group of nonionic surfactants are partial esters of polyols, in particular of C 3 -C 6 -polyols, such as, for example, glyceryl monoesters, partial esters of pentaerythritol or sugar esters, e.g.
  • Nonionic surfactants from the group of alkyl oligoglycosides are particularly skin-friendly and may therefore preferably be suitable in the context of the invention.
  • C 8 -C 22 -alkyl mono- and oligoglycosides their preparation and their use are known from the prior art. Their preparation is carried out in particular by reaction of glucose or oligosaccharides with primary alcohols having 8 to 22 C atoms, preferably 12 to 22, and particularly preferably 12 to 18 C atoms.
  • primary alcohols having 8 to 22 C atoms, preferably 12 to 22, and particularly preferably 12 to 18 C atoms.
  • the glycoside radical both monoglycosides in which a cyclic sugar residue is bonded glycosidically to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of up to preferably about 8 are suitable.
  • the degree of oligomerization here is a statistical mean based on a conventional distribution of homologues for such technical grade products Products which are available under the name Plantacare® contain a glucosidically bonded C 8 -C 16 -alkyl group on an oligoglucoside radical, the average degree of oligomerization of which is 1 to 2.
  • the acylglucamides derived from glucamine are also suitable as nonionic surfactants.
  • Nonionic surfactants preferably polyol and/or polyglycerol esters, are very particularly preferably present as co-surfactants in the agents according to the invention as component (c), and/or alkyl oligoglycosides.
  • the polyol component of these surfactants can be derived from substances which have at least two, preferably 3 to 12 and in particular 3 to 8 hydroxyl groups and 2 to 12 carbon atoms.
  • Typical examples are:
  • Reaction products based on polyglycerol are of particular importance because of their excellent use properties.
  • the acid component of these surfactants can be derived from straight-chain, branched, saturated and/or unsaturated carboxylic acids, optionally with functional groups, such as hydroxyl groups.
  • the acid component is particularly preferably fatty acids having 12 to 22 carbon atoms, which optionally carry a hydroxyl group, and in particular hydroxystearic acid.
  • the diester of polyhydroxystearic acid polyglyceryl 2-dipolyhydroxystearate, which is marketed, for example, by BASF Personal Care and Nutrition GmbH under the name Dehymus ® PGPH, is used as a glyceryl ester.
  • the further co-surfactants are conventionally present in an amount in the range of 0.5 to 25 weight-%; more preferably in the range of 3.0 to 18 weight-%; and particularly preferably in the range of 7 to 18 weight-%.
  • the sunscreen composition further comprises additives selected from the group consisting of thickener, active ingredients, preservatives and perfumes.
  • Suitable thickeners are anionic, zwitterionic, amphoteric and nonionic copolymers, such as, for example, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and esters thereof, acrylamidopropyltrimethylammonium chloride/acrylate copolymers, octylacrylamide/methyl methacrylate/tert-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate polymers, vinylpyrrolidone/vinyl acetate copolymers, vinylpyrrolidone/dimethylaminoethyl methacrylate/vinylcaprolactam terpolymers and optionally polysaccharides, in particular xanthan gum, guar and guar derivative
  • thickeners selected from the group of polyacrylates and crosslinked polyacrylates, such as Rheocare TTA®, Cosmedia® SP, Rheocare® C Plus, Tinovis® ADE, Tinovis® GTC, are added.
  • Thickeners from the group of polysaccharides, such as Ketro® T or Rheocare® XG, are furthermore preferred.
  • the amounts of thickener is in the range from 0.5 to 5 weight-%, in particular from 1. to 4 weight-%, calculated as active substance and based on total weight of the sunscreen composition.
  • the thickeners can be added to the concentrated agent before the dilution with water is carried out or can be contained in the water with which the dilution of the concentrated agent is carried out.
  • the concentrated agent is mixed with the thickener, and water for dilution is added to this mixture and the further formulation constituents are optionally stirred in.
  • the water, the thickener and optionally the other auxiliary substances are stirred with one another and the concentrated agent is added to this mixture.
  • the sunscreen final formulations prepared by the process according to the invention are often particularly finely divided 0/W emulsion having an average particle size of ⁇ 10 ⁇ m, preferably ⁇ 5 ⁇ m.
  • Biogenic active compounds which are suitable according to the invention are to be understood as meaning, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy)ribonucleic acid and fragmentation products thereof, 0-glucans, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts, such as e.g. Prunus extract, Bambara nut extract and vitamin complexes.
  • Such active compounds are employed in sunscreen final formulations as agents which trap free radicals, and serve to regenerate the skin.
  • Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the silver complexes known by the name Surfacine®.
  • Perfume oils which may be mentioned are natural, plant and animal as well as synthetic odoriferous substances or mixtures thereof. Natural odoriferous substances are obtained, inter alfa, by extraction of flowers, stems, leaves, fruit, fruit peel, roots and resins of plants. Animal raw materials are furthermore possible, such as, for example, civet and castoreum. Typical synthetic odoriferous compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Preferably, mixtures of various odoriferous substances which together generate a pleasant fragrance note are used.
  • the sunscreen final formulations further comprise auxiliary substances, such as moisture-retaining agents/skin-moisturizing agents, viscosity regulators, oils, fats and waxes, surfactants, pearlescent waxes, super-oiling agents, stabilizers, cationic, zwitterionic or amphoteric polymers, further UV filters, biogenic active compounds, film-forming agents, swelling agents, hydrotropic substances, preservatives, solubilizers, perfume oils, dyestuffs, insect repellant active compounds etc., which are listed below by way of example.
  • auxiliary substances such as moisture-retaining agents/skin-moisturizing agents, viscosity regulators, oils, fats and waxes, surfactants, pearlescent waxes, super-oiling agents, stabilizers, cationic, zwitterionic or amphoteric polymers, further UV filters, biogenic active compounds, film-forming agents, swelling agents, hydrotropic substances, preservatives, solubilizers, perfume oils, dyestuffs
  • Moisture-retaining agents serve to further optimize the sensory properties of the composition and for moisture regulation of the skin.
  • the moisture-retaining agents can be present in an amount in the range of 0 to 5.0 weight-%, based on total weight of the sunscreen composition.
  • Suitable substances are, inter alfa, amino acids, pyrrolidonecarboxylic acid, lactic acid and salts thereof, lactitol, urea and urea derivative, uric acid, glucosamine, creatinine, collagen cleavage products, chitosan or chitosan salts/derivatives, and in particular polyols and polyol derivatives (e.g.
  • glycerol diglycerol, triglycerol, ethylene glycol, propylene glycol, butylene glycol, erythritol, 1,2,6-hexanetriol, polyethylene glycols, such as PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, PEG-16, PEG-18, PEG-20), sugars and sugar derivatives (inter alia fructose, glucose, maltose, maltitol, mannitol, inositol, sorbitol, sucrose, sorbitylsilanediol, sucrose, trehalose, xylose, xylitol, glucuronic acid and salts thereof), ethoxylated sorbitol (sorbeth-6, sorbeth-20, sorbeth-30, sorbeth-40), honey and hardened honey, hardened starch hydrolysates and mixtures of hardened wheat protein and
  • Possible insect repellants are, for example, N,N-diethyl-m-toluamide, 1,2-pentanediol or 3-(N-n-butyl-N-acetylamino)propionic acid ethyl ester), which is marketed by Merck KGaA under the name Insect Repellent 3535, and butylacetylaminoproprionate. They are conventionally employed in the compositions according to the invention in an amount in the range of 0 to 6 weight-%, based on total weight of the sunscreen composition.
  • the viscosity of the agents according to the invention can be achieved by addition of viscosity regulators.
  • Possible viscosity regulators are, inter alfa, agents which impart consistency, such as e.g. fatty alcohols or hydroxy-fatty alcohols having 12 to 22 and preferably 16 to 18 carbon atoms and partial glycerides, fatty acids having 12 to 22 carbon atoms or 12-hydroxy-fatty acids.
  • a combination of these substances with alkyl oligoglucosides and/or fatty acid N-methylglucamides of the same chain length is also suitable, since such combinations deliver particularly stable and homogeneous emulsions.
  • the viscosity regulators also include thickening agents, such as, for example, Aerosil types (hydrophilic silicic acids), polysaccharides, in particular xanthan gum, guar-guar, agar-agar, alginates and tyloses, carboxymethylcellulose and hydroxyethyl- and hydroxypropylcellulose, furthermore higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates (e.g.
  • Bentonites such as e.g. Bentone® Gel VS-5PC (Rheox), which is a mixture of cyclopentasiloxane, Disteardimonium Hectorite and propylene carbonate, have also proved to be particularly effective.
  • Surfactants such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols, such as, for example, pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with a narrowed homologue distribution, alkyl oligoglucosides and electrolytes, such as e.g. sodium chloride and ammonium chloride, can also be employed for regulation of the viscosity.
  • fats and waxes are understood as meaning all lipids having a fat- or wax-like consistency which have a melting point above 20° C.
  • These include, for example, the classic triacylglycerols, that is to say the triesters of fatty acids with glycerol, which can be of plant or animal origin.
  • These can also be mixed esters, that is to say triesters of glycerol with various fatty acids, or a mixture of various glycerides.
  • These also include mixtures of mono-, di- and triglycerides.
  • So-called hardened fats and oils which are obtained by partial hydrogenation are particularly suitable according to the invention. Hardened fats and oils of plants are preferred, e.g.
  • Oxidation-stable plant glycerides which are available under the name Cegesoft ® or Novata ® are particularly suitable.
  • Possible waxes are, inter alfa, natural waxes, such as e.g. candelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax), uropygium fat, ceresin, ozocerite (earth wax), petrolatum, paraffin waxes, microwaxes; chemically modified waxes (hard waxes), such as e.g. montan ester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes, such as e.g. polyalkylene waxes and polyethylene glycol waxes.
  • natural waxes such as e.g. candelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax, gua
  • fat-like substances such as lecithins and phospholipids
  • Lecithins are glycero-phospholipids which are formed from fatty acids, glycerol, phosphoric acid choline by esterification, and are often also called phosphatidylcholines (PC).
  • Cephalins which are also called phosphatidic acids and are derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids, may be mentioned as an example of natural lecithins.
  • phospholipids are usually understood as meaning mono- and preferably diesters of phosphoric acid with glycerol (glycerol phosphates). Sphingosines and sphingolipids are also possible as fat-like substances.
  • Suitable pearlescent waxes are, for example, alkylene glycol esters, specifically ethylene glycol distearate; fatty acid alkanolamides, specifically coconut fatty acid diethanolamide; partial glycerides, specifically stearic acid monoglyceride; esters of polybasic, optionally hydroxy-substituted carboxylic acids with C 6 -C 22 -fatty alcohols, specifically long-chain esters of tartaric acid; fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty alde-hydes, fatty ethers and fatty carbonates, which have at least 24 carbon atoms in total—specifically Lauron®; distearyl ether; fatty acids, such as stearic acid, C 12 -C 22 -hydroxy-fatty acids, behenic acid, ring-opening products of C 12 -C 22 -olefin epoxides with C 12 -C 22 -fatty alcohols and/or polyols
  • Super-oiling agents which can be used are substances such as, for example, lanolin and lecithin and polyethoxylated or acylated derivatives of lanolin and lecithin, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter simultaneously serving as foam stabilizers.
  • stabilizers which can be employed are metal salts of fatty acids, such as e.g. magnesium, aluminum and/or zinc stearate or ricinoleate.
  • Suitable cationic polymers which further optimize the sensory properties of the compositions according to the invention and impart to the skin a sensation of softness are, for example, cationic cellulose derivatives, such as e.g. a quaternized hydroxyethylcellulose which is obtainable from Amerchol under the name Polymer JR 400®, cationic starch, copolymers of di-allylammonium salts and acrylamides, quaternized vinylpyrrolidone/vinylimidazole polymers, such as e.g.
  • Luviquat® condensation products of polyglycols and amines, quaternized collagen polypeptides, such as, for example, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen (Lamequat® L/Griinau), quaternized wheat polypeptides, polyethylenimine, cationic silicone polymers, such as e.g.
  • amodimethicone copolymers of adipic acid and dimethylamino-hydroxypropyldiethylenetriamine (Cartaretine®/Sandoz), copolymers of acrylic acid with di-methyldiallylammonium chloride (Merquat® 550/Chemviron, polyaminopolyamides and crosslinked water-soluble polymers thereof, cationic chitin derivatives, such as, for example, quaternized chitosan, condensation products, optionally distributed in microcrystalline form, of dihaloalkyls, such as e.g. dibromobutane with bisdialkylamines, such as e.g.
  • cationic guar gum such as e.g. Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers, such as e.g. Mirapol0 A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol.
  • Starch derivative can furthermore be employed to improve the skin sensation, e.g. Dry Flo® PC (INCI: Aluminum Starch Octenylsuccinate).
  • Suitable silicone compounds have already been mentioned with the oily substances.
  • dimethylpolysiloxanes methylphenylpolysiloxanes and cyclic silicones
  • amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds which can be either liquid or resinous at room temperature
  • Simethicones which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units and silicon dioxide or hydrogenated silicates, are furthermore suitable.
  • So-called film-forming agents which lead to a further improvement in the sensory properties of the preparations according to the invention are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, collagen, hyaluronic acid and salts thereof and similar compounds, and the polyvinylpyrrolidones, vinylpyrrolidone/vinyl acetate copolymers, polymers of the acrylic acid series and quaternized cellulose derivatives already mentioned under the viscosity regulators.
  • hydrotropic substances such as, for example, ethanol, isopropyl alcohol, or polyols
  • polyols which are possible here have preferably 2 to 15 carbon atoms and at least two hydroxyl groups.
  • the polyols can also contain further functional groups, in particular amino groups, or can be modified with nitrogen.
  • Dyestuffs which can be used are the substances which are suitable and approved for cosmetic purposes.
  • Patent Blue V is 2-[(4-diethylaminophenyl)(4-diethylimino-2,5-cyclohexadien-1-ylidene)methyl]-4-hydroxy-1,5-benzene-disulfonate, and is available from Sigma Aldrich.
  • Benzophenone-4 is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid is available from BASF.
  • SunsH® 130 is available from Sunjin Beauty Science (formerly Sunjin Chemical)
  • Particle size is synonymous with particle diameter and was determined by scanning electron microscopy (SEM) or transmission electron microscopy (TEM).
  • Average porosity and average pore diameter Mercury porosimetry analysis was used to characterize the porosity of the spheres. Mercury porosimetry applies controlled pressure to a sample immersed in mercury. External pressure is applied for the mercury to penetrate into the voids/pores of the material. The amount of pressure required to intrude into the voids/pores is inversely proportional to the size of the voids/pores. The mercury porosimeter generates volume and pore size distributions from the pressure versus intrusion data generated by the instrument using the Washburn equation. For example, porous silica spheres containing voids/pores with an average size of 165 nm have an average porosity of 0.8.
  • the determination of the in vitro SPF is performed by measuring the diffuse transmission in the UV-range using a Labsphere Ultraviolet Transmittance Analyzer 2000S. In order to simulate the inhomogeneous surface structure of human skin, substrates with rough or porous surface are taken for such measurements. For this method Sandblasted 4-5 ⁇ m PMMA (PolyMethylMethacrylate) plates, from Helioscience (France), are used as substrate.
  • PMMA PolyMethylMethacrylate
  • the sunburn protection factor (SPF) formalism was first introduced by Sayre in 1979 [1], by which an average of the inverse transmission (1/T) of the respective sunscreen in the spectral range between 290 and 400 nm is calculated, including weighting with the irradiance spectrum of a UV source, Ss( ⁇ ), and the erythema) action spectrum, Ser( ⁇ ):
  • Transparency/whitening method Color measurements were performed with the prepared compositions applied on PMMA plates also used for in vitro SPF measurement. From the obtained L*a*b* parameters L* refers to the lightness of a sample. The difference of L* to a blank sample is expressed as delta L* and can be used to compare the transparency or whitening of the samples.
  • a styrene/acrylic acid copolymer was prepared as follows: 230 mL Deionized (DI) water was added to a 3-neck reaction flask equipped with a thermometer, condenser, magnetic stirring and nitrogen atmosphere. The water was heated to 80° C. and 10 g of styrene was added with stirring, followed by addition of 100 mg acrylic acid dissolved in 10 mL DI water via syringe. 100 mg of ammonium persulfate was dissolved in 10 mL DI water and added to the stirred mixture via syringe. The reaction mixture was stirred for 24 hours at 80° C. The polymer colloid dispersion was allowed to cool to room temperature and was purified via centrifugation, producing polystyrene nanospheres having an average particle size of 250 nm.
  • DI Deionized
  • the aqueous polystyrene colloid dispersion was diluted to 1 weight-% with deionized water and 1 weight-% silica nanoparticles were added and the mixture was sonicated to prevent particle agglomeration.
  • a continuous oil phase used was 0.1 weight-% polyethylene glycol/perfluoropolyether surfactant in a fluorinated oil.
  • the aqueous colloid dispersion and oil were each injected into a microfluidic device having a 50 ⁇ m droplet junction via syringes associated with pumps. The system was allowed to equilibrate until monodisperse droplets were produced. The monodisperse droplets were collected in a reservoir.
  • collected droplets were dried in an oven at 45° C. for 4 hours to provide monodisperse polymer template spheres.
  • the polymer template spheres were calcined by placing on a silicon wafer, heating from room temperature to 500° C. over a 3 hours period, holding at 500° C. for 2 hours, and cooling back to room temperature over a 3 hours period to obtain monodisperse porous silica spheres having an average diameter of 15 microns. These porous silica spheres having average diameter of 15 ⁇ m were porous silica microspheres.
  • the average pore (void) diameter of the silica spheres was 170 nm and the average porosity was 0.8.
  • the drying step can be performed employing microwave irradiation, drying under vacuum and/or drying in the presence of a desiccant.
  • Example 1 The product of Example 1 was physically mixed with an aqueous dispersion of carbon black or with a carbon black powder at varying weight levels. Monodisperse porous silica spheres containing carbon black at levels of 0.5 weight-%, 1 weight-%, 2 weight-%, 3 weight-%, 4 weight-% and 5 weight-%, based on the total weight of the spheres were obtained.
  • a styrene/acrylic acid copolymer was prepared as follows: 230 mL Deionized (DI) water was added to a 3-neck reaction flask equipped with a thermometer, condenser, magnetic stirring and nitrogen atmosphere. The water was heated to 80° C. and 10 g of styrene was added with stirring, followed by 100 mg acrylic acid dissolved in 10 mL DI water via syringe. 100 mg of ammonium persulfate was dissolved in 10 mL DI water and added to the stirred mixture via syringe. The reaction mixture was stirred for 24 hours at 80° C.
  • DI Deionized
  • the polymer colloid dispersion was allowed to cool to room temperature and was purified via centrifugation, producing polystyrene nanospheres having an average particle size of 250 nm.
  • the aqueous polystyrene colloid dispersion was diluted to 1 weight-% with deionized water and 1 weight-% silica nanoparticles were added and the mixture was sonicated to prevent particle agglomeration.
  • the aqueous dispersion was spray-dried to provide polymer template spheres comprising polymer nanospheres and silica.
  • the spheres are calcined by heating from room temperature to 500° C. over a 3 hours period, holding at 500° C.
  • porous silica spheres having an average diameter of 15 microns.
  • the average pore (void) diameter of the silica spheres was 170 nm and the average porosity was 0.8.
  • a sample of porous silica spheres was prepared according to the procedure of example 3.
  • the polymer nanospheres having an average particle size of 421 nm were used and a weight ratio of the polymer to silica was 3:1.
  • FIG. 1 shows SEM image of the porous silica sphere obtained according to example 4.
  • the average porosity of the silica spheres was 0.8.
  • a sample of porous silica spheres was prepared according to the procedure of example 3.
  • the polymer nanospheres having an average particle size of 421 nm were used and a weight ratio of the polymer to silica was 3:1.
  • FIG. 2 shows SEM image of a porous silica sphere obtained according to example 5.
  • the average porosity of the silica spheres was 0.8.
  • a sample of porous zinc oxide spheres was prepared according to the procedure of Example 3, wherein silica was replaced with zinc oxide.
  • the polystyrene nanospheres having an average diameter of 230 nm were used and a weight ratio of the polymer to zinc oxide was 1:2.
  • a sample of porous titania spheres was prepared according to the procedure of example 3, wherein silica was replaced with titania.
  • the polymer nanospheres having an average particle size of 170 nm were used and a weight ratio of the polymer to titania was 3:1.
  • FIG. 3 shows SEM image of a porous titania sphere obtained according example 7.
  • the average porosity of the titania spheres was 0.8.
  • Porous titania spheres were prepared by procedure similar to example 7.
  • the polymer nanospheres having an average particle size of 285 nm were used and a weight ratio of the polymer to titania was 3:1.
  • FIG. 4 shows SEM image of a porous titania sphere obtained according example 8.
  • the average porosity of the titania spheres was 0.8.
  • Porous Spheres Comprising Silica and Titania
  • Porous spheres containing silica and titania were prepared according to the process of Example 3, wherein the weight ratio of polymer to the total metal oxide was 3:1. The weight ratio of silica to titania was 9:1.
  • Step 1) Polymer spheres having at least two different average particle sizes:
  • a styrene/acrylic acid copolymer was prepared as follows: 230 mL deionized (DI) water was added to a 3-neck reaction flask equipped with a thermometer, condenser, magnetic stirring and nitrogen atmosphere. The water was heated to 80° C. and 10 g of styrene was added with stirring, followed by 100 mg acrylic acid dissolved in 10 mL DI water via syringe. 100 mg of ammonium persulfate was dissolved in 10 mL DI water and added to the stirred mixture via syringe. The reaction mixture was stirred for 24 hours at 80° C. The polymer colloid dispersion was allowed to cool to room temperature and was purified via centrifugation, producing polystyrene nanospheres having an average particle size of 250 nm.
  • DI deionized
  • styrene/acrylic acid copolymer was prepared to produce polystyrene nanospheres having an average particle size of 350 nm.
  • the first aqueous polystyrene colloid dispersion (250 nm) was mixed with the second aqueous polystyrene colloid dispersion (350 nm) in a weight ratio of 7:3 and the mixture was diluted to 1 weight-% with deionized water and was sonicated to prevent particle agglomeration.
  • the continuous oil phase used was 0.1 weight-% polyethylene glycol/perfluoropolyether surfactant in a fluorinated oil.
  • the aqueous colloid dispersion mixture and oil were each injected into a microfluidic device having a 50 ⁇ m droplet junction via syringes associated with pumps. The system was allowed to equilibrate until monodisperse droplets were produced. The monodisperse droplets were collected in a reservoir.
  • the monodisperse polystyrene spheres comprise polystyrene nanospheres having a bimodal particle size distribution.
  • Step 2 Porous metal oxide spheres
  • Example 1 was repeated, adding 1 weight-% silica nanoparticles to the aqueous mixture of first and second colloid dispersions prior to mixing with the oil phase to form a water-in-oil emulsion.
  • the collected droplets from the microfluidic device were dried as in Example 1 to form polymer template spheres.
  • the polymer template spheres were calcined by placing on a silicon wafer, heating from room temperature to 500° C. over a 3 hours period, holding at 500° C. for 2 hours, and cooling back to room temperature over a 3 hours period.
  • monodisperse silica spheres having an average diameter of 15 microns, containing two different average pore sizes.
  • a styrene/acrylic acid copolymer was prepared as follows: 230 mL deionized (DI) water was added to a 3-neck reaction flask equipped with a thermometer, condenser, magnetic stirring and nitrogen atmosphere. The water was heated to 80° C. and 10 g of styrene are added with stirring, followed by 100 mg acrylic acid dissolved in 10 mL DI water via syringe. 100 mg of ammonium persulfate was dissolved in 10 mL DI water and added to the stirred mixture via syringe. The reaction mixture was stirred for 24 hours at 80° C. The polymer colloid dispersion was allowed to cool to room temperature and was purified via centrifugation, producing polystyrene nanospheres having an average particle size of 250 nm.
  • DI deionized
  • styrene/acrylic acid copolymer was prepared to produce polystyrene nanospheres having an average particle size of 350 nm.
  • the first aqueous polystyrene colloid dispersion 250 nm was mixed with the second agueous polystyrene colloid dispersion (350 nm) in a weight ratio of 7:3 and the mixture was diluted to 1 weight-% with deionized water and 1 weight-% silica nanoparticles are added to the mixture which was sonicated to prevent particle agglomeration.
  • the aqueous dispersion was spray-dried to provide polymer template spheres comprising monodisperse polymer nanospheres having bimodal distribution and silica.
  • the spheres were calcined by heating from room temperature to 500° C. over a 3 hours period, holding at 500° C. for 2 hours, and cooling back to room temperature over a 3 hours period to obtain porous silica spheres.
  • a sample of porous zinc oxide spheres were prepared according to the process of Example 11, where the polystyrene nanospheres having average particle sizes of 250 nm and 320 nm were used in a weight ratio of 1:1, and where the weight ratio of the polymer to zinc oxide was 1:2.
  • Porous Spheres Comprising Silica and Titania having Two Average Particle Sizes
  • a sample of porous spheres containing silica and titania was prepared according to the process of Example 11, where the polystyrene nanospheres have average particle sizes of 350 nm and 460 nm were used in a weight ratio of 1:4 and wherein the weight ratio of the polymer to total metal oxide was 3:1.
  • the weight ratio of silica to titania was 9:1.
  • the porous microspheres comprising silica according to example 3 were dispersed in aqueous solutions of a water-soluble dye.
  • the dispersions were filled into quartz cuvettes (Hellma Analytics) of 0.1 cm optical thickness and the absorbance was measured with a Perkin Elmer Lambda 20 UV/vis spectrometer having an integration sphere accessory (RSA-PE-20), which collected the direct transmitted light and also the light scattered in forward direction.
  • RSA-PE-20 integration sphere accessory
  • the integration sphere accessory is a single beam device.
  • Reference and sample dispersion cells were placed in the light beam at the transmittance port of the integration sphere, while a reflectance standard was mounted at the reflectance port of the sphere. Measurements were performed with a spectral resolution of 2 nm. First the absorbance of the reference dispersion was recorded and then that the corresponding sample was recorded.
  • FIG. 5 shows the absorbance of aqueous dispersions comprising Patent Blue V at a constant concentration (5.5 ⁇ 10 ⁇ 6 mol/L) at an optical pathlength d of 0.1 cm in the presence of the porous silica spheres according to example 3.
  • 1 refers to the absorption spectrum of reference sample
  • 2 refers to the absorption spectrum of aqueous dispersions comprising the porous silica spheres at a concentration of 2 wt %
  • 3 refers to the absorption spectrum of aqueous dispersions comprising the porous silica spheres at a concentration of 5 wt %.
  • porous silica spheres increases the efficacy of the dye absorbance, and the absorbance increases by a factor of about 1.5 at 5 weight-% porous microsphere concentration.
  • the procedure for experiment 2 was similar to that of experiment 1, except that a water-soluble UV-absorber Benzophenone-4 was used instead of Patent Blue V.
  • the chemical name of this UV-absorber is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid.
  • FIG. 6 shows the absorbance of aqueous dispersions comprising Benzophenone-4 at a constant concentration of 5.18 ⁇ 10 5 mol/L, at an optical pathlength d of 0.1 cm in the presence of the porous silica spheres according to example 3.
  • 1 refers to the absorption spectrum of reference sample
  • 2 refers to the absorption spectrum of aqueous dispersions comprising the porous silica spheres at a concentration of 2 wt %
  • 3 refers to the absorption spectrum of aqueous dispersions comprising the porous silica spheres at a concentration of 5 wt %.
  • porous silica spheres increases the efficacy of the UV absorbance of benzophenone-4, and the absorbance of UV radiations increases by a factor of about 2.5 at 5 wt % porous silica spheres concentration.
  • the boosting of absorbance i.e. increase in the absorbance due to the presence of porous spheres, is greater in the UV range as compared to the visible range.
  • a set of five aqueous dispersions containing Benzophenone-4 and different concentrations of porous silica particles of example 3 was prepared by a procedure similar to experiment 2. Similarly, one set each of aqueous dispersion comprising different concentrations of porous silica particles of examples 4 and 5 each were prepared. A blank sample, which did not contain any porous metal oxide particles, was prepared for comparison. The UV absorbance was measured for the aqueous dispersions at the ⁇ max of the UV absorber.
  • FIG. 7 shows a graph plotted for the absorbance of aqueous dispersions comprising Benzophenone-4 at an optical pathlength d of 0.1 cm at various concentrations of the porous silica spheres according to examples 3, 4 and 5.
  • 1 refers to the absorption spectrum of aqueous dispersions comprising the porous silica spheres of example 3
  • 2 refers to the absorption spectrum of aqueous dispersions comprising the porous silica spheres of example 4
  • 3 refers to the absorption spectrum of aqueous dispersions comprising the porous silica spheres of example 5
  • blank refers to the absorbance of the blank sample.
  • a set of five aqueous dispersions containing Benzophenone-4 and different concentrations of the commercially available silica particles Sunsil® 130 from Sunjin was prepared by the procedure to experiment 2.
  • a blank sample which did not contain the porous metal oxide particles was prepared for comparison.
  • the UV absorbance was measured for the aqueous dispersions at the ⁇ max of the UV absorber.
  • FIG. 8 shows a graph plotted for the absorbance of aqueous dispersions comprising Benzophenone-4 at an optical pathlength d of 0.1 cm at various concentrations silica particles Sunsil® 130 at various concentrations.
  • 1 refers to the absorption spectrum of aqueous dispersions comprising the Sunsil® 130 silica particles; and blank refers to the absorbance of the blank sample.
  • FIG. 9 shows the visible range absorption spectrum of the aqueous dispersions in the presence of the porous titania spheres according to examples 7 and 8 at a concentration of 0.2 wt % and 0.5 wt %, at an optical pathlength d of 0.1 cm.
  • 1 refers to the absorption spectrum of aqueous dispersions comprising the porous titania spheres of example 8 at a concentration of 0.5 wt %
  • 2 refers to the absorption spectrum of aqueous dispersions comprising the porous titania spheres of example 7 at a concentration of 0.5 wt %
  • 3 refers to the absorption spectrum of aqueous dispersions comprising the porous titania spheres of example 8 at a concentration of 0.2 wt %
  • 4 refers to the absorption spectrum of aqueous dispersions comprising the porous titania spheres of example 7 at a concentration of 0.2 wt %
  • 5 refers to the absorbance of the reference sample which do not contain any porous metal oxide spheres.
  • porous titania spheres increases the efficacy of the dye absorbance, and the absorbance increases by a factor of about 2.8 and 4 at 5 weight-% porous microsphere concentration of the porous titania shperes from examples 7 and 8 respectively.
  • porous titania spheres prepared according to examples 7 and 9 were dispersed in aqueous solutions which do not contain any dye or UV-absorber. The UV-absorption of these solutions was analysed in a manner similar to experiment 1.
  • FIG. 10 shows the UV absorption spectrum of the aqueous dispersions comprising the porous titania spheres according to examples 7 and 8 at a concentration of 0.2 wt % and 0.5 wt % each, at an optical pathlength d of 0.1 cm.
  • 1 refers to the absorption spectrum of aqueous dispersions comprising the porous titania spheres of example 7 at a concentration of 0.4 wt %
  • 2 refers to the absorption spectrum of aqueous dispersions comprising the porous titania spheres of example 8 at a concentration of 0.4 wt %
  • 3 refers to the absorption spectrum of aqueous dispersions comprising the porous titania spheres of example 7 at a concentration of 0.2 wt %
  • 4 refers to the absorption spectrum of aqueous dispersions comprising the porous titania spheres of example 8 at a concentration of 0.2 wt %.
  • the aqueous dispersion comprising porous titania spheres shows a broad UV absorbance in the range from 250 to 390 nm with the maximum UV absorbance in the range of 320 to 340 nm.
  • the absorption is high in the UVB range of 290 to 320 nm, whereas the absorption shows a steep decrease in the UVA range of 380 to 420 nm.
  • compositions For the determination of SPF, two sets of compositions were prepared. The first set of compositions were prepared with UV filters in the oil phase and the second set of compositions was prepared without additional UV filter.
  • compositions were prepared:
  • Phase A and phase B were separately heated with stirring. Phase A was incorporated to phase B under stirring. The mixture was stirred till a homogeneous mixture was obtained, followed by stirring for 1 min. Finally, the mixture is cooled under stirring to room temperature.
  • the basic formulation was prepared at 80° C.
  • Two formulations were prepared using 2 weight-% and 5.5 weight-% of porous spheres according to example 3 respectively.
  • the porous spheres were incorporated under stirring in the basic formulation and filled up with water ad 100.
  • Reference formulation The reference sample was prepared using the market product “SunSpheres®” from Dow Chemicals. The 5.5 weight-% of the market product was incorporated in the basic formulation. Sunspheres® are a styrene-acrylate copolymer with a hollow sphere morphology prepared via controlled emulsion polymerization.
  • Placebo formulation The placebo sample without particles was prepared by adding water to the basic formulation ad 100.
  • FIG. 11 shows the absorbance of the compositions 5, 6, 8 and 9 in the wavelength range of 290 to 450 nm.
  • the placebo sample without particles was prepared by adding water to the basic formulation ad 100.
  • Three formulations were prepared using 2 weight-%, 5.5 weight-% and 8-weight % of porous silica spheres according to example 3, respectively.
  • the porous spheres were incorporated with water in the basic formulation.
  • Reference formulation The reference sample was prepared using the market product “Sun-Spheres®” from Dow Chemicals. The 5.5 weight-% the market product was incorporated in the basic formulation.
  • FIG. 12 shows the absorbance of the compositions without an additional UV filter in the range from 290 to 450 nm.
  • 1 refers to the absorption spectrum of composition 3
  • 2 refers to the absorption spectrum of composition 2
  • 3 refers to the absorption spectrum of composition 1
  • 4 refers to the absorption spectrum of placebo composition.
  • compositions with 5,5 weight-% or 8 weight-% of added particles show increased absorption over the whole UV range from 290 to 450nm.
  • the in vitro SPF of the composition could be increased by 10% with addition of 5,5 weight-% of porous spheres according to example 3 and by 20% with addition of 8 weight-% of porous spheres according to example 3.
  • the whitening data were determined for both formulation series prepared in experiment 3 by color measurement as described above.
  • FIG. 13 The results for formulations with UV-filters are summarized in FIG. 13 .
  • 1 refers to the absorption spectrum of composition 9; 2 refers to the absorption spectrum of composition 5; 3 refers to the absorption spectrum of composition 6; and 4 refers to the absorption spectrum of placebo composition 8.
  • FIG. 14 The results for formulations without UV-filters are summarized in FIG. 14 .
  • 1 refers to the absorption spectrum of placebo composition
  • 2 refers to the absorption spectrum of composition 1
  • 3 refers to the absorption spectrum of composition 2
  • 4 refers to the absorption spectrum of composition 3
  • 5 refers to the absorption spectrum of composition 4 containing the reference composition.

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WO2023139038A1 (en) * 2022-01-18 2023-07-27 Basf Se Uv filter compositions comprising hybrid metal oxide particles
FR3131838A1 (fr) 2022-01-18 2023-07-21 Basf Beauty Care Solutions France Sas Nouvelle utilisation cosmétique de sphères poreuses à porosité fermée d’oxyde métallique
WO2023139037A1 (en) * 2022-01-18 2023-07-27 Basf Se Uv filter compositions comprising closed-cell metal oxide particles

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FR2847464B1 (fr) * 2002-11-21 2006-03-17 Oreal Composition antisolaire vaporisable a base de microparticules spheriques de silice poreuse et dispositifs de pressurisation la contenant
WO2014203913A1 (en) * 2013-06-18 2014-12-24 L'oreal Cosmetic composition
WO2015044306A1 (en) * 2013-09-30 2015-04-02 Dsm Ip Assets B.V. Topical sun screen compositions titanium dioxide and silica
TWI561251B (en) * 2015-07-31 2016-12-11 Univ Nat Tsing Hua Sun protection composition and application the same

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KR20210137124A (ko) 2021-11-17
BR112021017253A2 (pt) 2021-11-09

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